The compounds of the formula I ##STR1## where R is unsubstituted or substituted phenyl or naphthyl, R1 and R2 are each unsubstituted or substituted alkyl, alkenyl or cycloalkyl, and one of the radicals may furthermore be hydrogen, R3 is hydrogen, methyl, methoxy, ethoxy or chlorine, and R4 is acylamino, are particularly useful for dyeing polyesters.
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1. A compound of the formula ##STR12## where R is phenyl or naphthyl; R1 and R2 are each selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3,-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonyloxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-β-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl and 2-benzoylethyl, and one of R1 and R2 may be hydrogen,
R3 is hydrogen, methyl, methoxy, ethoxy or chlorine and R4 is selected from the group consisting of methylcarbonylamino, ethylcarbonylamino, n- and iso-propylcarbonylamino, n-, iso- and sec-butylcarbonylamino, benzylcarbonylamino, benzoylamino, o-, m- and p-methylbenzoylamino, o-, m- and p-chlorobenzoylamino, o-, m- and p-methoxybenzoylamino, o-, m- and p-nitrobenzoylamino, methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino, methoxymethylcarbonylamino and ethoxy-, phenoxy-, cyano-, chloro- and bromomethylcarbonylamino.
2. A compound as claimed in
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The present invention relates to compounds of general formula I ##STR2## where R is unsubstituted or substituted phenyl or naphthyl, R1 and R2 are each unsubstituted or substituted alkyl, alkenyl or cycloalkyl, and one of the radicals may furthermore be hydrogen, R3 is hydrogen, methyl, methoxy, ethoxy or chlorine and R4 is acylamino.
The radicals R may be substituted by, for example, fluorine, chlorine, bromine, trifluoromethyl, C1 -C4 -alkyl or -alkoxy, nitro or cyano, chlorine, methyl and methoxy being preferred.
R1 and R2 are each, for example, C1 -C6 -alkyl which may furthermore be substituted by hydroxyl, C1 -C4 -alkoxy, phenoxy, phenyl, cyano, alkanoyl, alkanoyloxy, alkoxycarbonyl, aroyloxy, alkoxycarbonyloxy, alkylaminocarbonyloxy, arylaminocarbonyloxy or alkoxy-alkoxy, or are each C2 -C4 -alkenyl or C5 -C7 -cycloalkyl.
Specific examples of radicals R1 and R2 are methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonyloxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-β-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl and 2-benzoylethyl, and one of the radicals may furthermore be hydrogen.
Examples of suitable radicals R4 are unsubstituted or substituted C1 -C6 -alkanoylamino, unsubstituted or substituted benzoylamino and C1 -C4 -alkylsulfonylamino or -dialkylaminosulfonylamino.
Specific examples of radicals R4 are methylcarbonylamino, ethylcarbonylamino, n- and isopropylcarbonylamino, n-, iso- and sec-butylcarbonylamino, benzylcarbonylamino, benzoylamino, o-, m- and p-methylbenzoylamino, o-, m- and p-chlorobenzoylamino, o-, m- and p-methoxybenzoylamino, o-, m- and p-nitrobenzoylamino, methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino, methoxymethylcarbonylamino and ethoxy-, phenoxy-, cyano-, chloro- and bromomethylcarbonylamino.
The compounds of the formula I can be prepared by reacting a diazonium salt of a compound of the formula I ##STR3## with a coupling component of the formula ##STR4## by a conventional method. The Examples which follow illustrate the preparation. Parts and percentages are by weight, unless stated otherwise.
The compounds of the formula I are preferably used for dyeing synthetic polyesters; essentially blue hues are obtained, some of them possessing very good fastness properties.
Of particular importance are compounds of the formula I in which R is phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy or ethoxy, R1 and R2 are each allyl, benzyl, phenylethyl or C1 -C4 -alkyl which is unsubstituted or substituted by hydroxyl, cyano, C1 -C4 -alkanoyloxy, C1 -C4 -alkoxycarbonyl or C1 -C4 -alkoxy, and one of the radicals may furthermore be hydrogen, R3 is hydrogen, methyl, methoxy or ethoxy and R4 is C1 -C4 -alkanoylamino, methoxy-, ethoxy-, phenoxy-, cyano- or chloromethylcarbonylamino, C1 -C4 -alkylsulfonylamino or benzoylamino.
22.8 parts of 2-amino-3-cyano-4-phenyl-5-formylthiophene were introduced into a mixture of 150 parts by volume of glacial acetic acid/propionic acid (3:1) and 50 parts by volume of 85% strength sulfuric acid. 17.5 parts by volume of nitrosylsulfuric acid (11.5% of N2 O3) were added dropwise at 0°-5°C, after which the mixture was stirred for 4 hours at this temperature.
24.6 parts of 3-diethylaminoacetanilide were dissolved in 100 parts by volume of dimethylformamide, and the solution was added to 250 parts of water, 50 parts by volume of 32% strength hydrochloric acid, 1000 parts of ice and 2.5 parts of amidosulfonic acid. The diazo solution obtained beforehand was added in the course of 0.5 hour, with external cooling with ice/water, and the mixture was stirred for 4 hours at 0°-5° C. and overnight without further cooling. The product was filtered off under suction, washed neutral with water and dried at 60°C in a drying oven under reduced pressure to give 38 parts of a blueish black powder of the formula ##STR5## which dyes polyesters in fast blue hues.
The dyes defined in the Table below were obtained by a similar method.
| __________________________________________________________________________ |
| ##STR6## |
| Example No. |
| R R1 R2 R3 |
| R4 Color on |
| __________________________________________________________________________ |
| PES |
| 2 C6 H5 |
| CH2 CHCH2 |
| CH2 CHCH2 |
| H NHCOCH3 |
| blue |
| 3 C6 H5 |
| CH2 CHCH2 |
| CH2 CHCH2 |
| H NHCOC6 H5 |
| blue |
| 4 C6 H5 |
| C2 H5 |
| C2 H5 |
| H NHCOC6 H5 |
| blue |
| 5 C6 H5 |
| C4 H9 (n) |
| C4 H9 (n) |
| H NHCOCH3 |
| blue |
| 6 C6 H5 |
| C6 H13 (n) |
| C6 H13 (n) |
| H NHCOCH3 |
| blue |
| 7 C6 H5 |
| C2 H4 OCOCH3 |
| C2 H4 OCOCH3 |
| H NHCOCH3 |
| blueish violet |
| 8 C6 H5 |
| C2 H4 OCOCH3 |
| C2 H4 OCOCH3 |
| H NHCOC6 H5 |
| blueish violet |
| 9 C6 H5 |
| C2 H4 CN |
| CH2 CHCH2 |
| H NHCOC6 H5 |
| blueish violet |
| 10 C6 H5 |
| C2 H4 CN |
| C4 H9 (n) |
| H NHCOC6 H5 |
| blue |
| 11 C6 H5 |
| C2 H4 CN |
| ##STR7## H NHCOC6 H5 |
| blueish violet |
| 12 C6 H5 |
| C2 H4 OCH3 |
| C2 H4 CN |
| H NHCOCH3 |
| blue |
| 13 C6 H5 |
| CH2 CO2 CH3 |
| CH2 CO2 CH3 |
| CH3 |
| NHSO2 CH3 |
| blueish violet |
| 14 C6 H5 |
| H C2 H4 CO2 C2 H4 |
| OC6 H5 |
| H NHCOCH3 |
| blueish violet |
| 15 C6 H5 |
| H C2 H4 OC2 H5 |
| Cl NHCOCH3 |
| blue |
| 16 C6 H5 |
| C2 H 4 CN |
| CH2 CHCH2 |
| OCH3 |
| NHCOCH3 |
| greenish blue |
| 17 C6 H5 |
| C2 H4 OCOCH3 |
| C2 H4 CO2 CH3 |
| H NHCOCH3 |
| violet |
| 18 C6 H5 |
| C2 H4 OH |
| C2 H4 CO2 CH3 |
| H NHCOCH3 |
| blue |
| 19 C6 H5 |
| C2 H4 OH |
| CH2 C6 H5 |
| H NHCOCH3 |
| blue |
| 20 C6 H5 |
| C2 H4 OCOCH3 |
| CH2 C6 H5 |
| H NHCOCH3 |
| blue |
| 21 C6 H5 |
| CH2 CHCH2 |
| CH2 CHCH2 |
| OCH3 |
| NHCOCH3 |
| greenish blue |
| 22 C6 H5 |
| C2 H4 OCOCH3 |
| C2 H4 OCOCH3 |
| OCH3 |
| NHCOCH3 |
| greenish blue |
| 23 C6 H5 |
| H C2 H4 CO2 C4 H9 |
| OCH3 |
| NHCOCH3 |
| greenish blue |
| 24 C6 H5 |
| H C2 H4 CO2 C2 H4 |
| OC4 H9 |
| H NHCOCH3 |
| reddish blue |
| 25 p-CH3 OC6 H4 |
| C 2 H5 |
| C2 H5 |
| H NHCOCH3 |
| blue |
| 26 p-CH3 OC6 H4 |
| CH2 CHCH2 |
| CH2 CHCH2 |
| H NHCOCH3 |
| blue |
| 27 p-CH3 OC6 H4 |
| C4 H9 (n) |
| C4 H9 (n) |
| H NHCOCH3 |
| blue |
| 28 p-CH3 OC6 H4 |
| C6 H13 (n) |
| C6 H13 (n) |
| H NHCOCH3 |
| blue |
| 29 p-CH3 OC6 H4 |
| CH2 CHCHCl |
| CH2 CHCHCl |
| H NHCOCH3 |
| reddish blue |
| 30 p-CH3 OC6 H4 |
| C2 H4 CN |
| C4 H9 (n) |
| H NHCOC6 H5 |
| blue |
| 31 p-CH3 OC6 H4 |
| C2 H4 OCOCH3 |
| C2 H4 OCOCH3 |
| H NHCOC6 H5 |
| reddish blue |
| 32 p-CH3 OC6 H4 |
| C2 H4 CN |
| CH2 CHCH2 |
| OCH3 |
| NHCOCH3 |
| greenish blue |
| 33 p-CH3 OC6 H4 |
| CH2 CHCH2 |
| CH2 CHCH2 |
| OCH3 |
| NHCOCH3 |
| greenish blue |
| 34 p-ClC 6 H4 |
| C2 H5 |
| C2 H5 |
| H NHCOCH3 |
| blue |
| 35 p-ClC6 H4 |
| CH2 CHCHCl |
| CH2 CHCHCl |
| H NHCOCH3 |
| reddish blue |
| 36 p-ClC6 H4 |
| C6 H13 (n) |
| C6 H13 (n) |
| H NHCOCH3 |
| blue |
| 37 p-ClC6 H4 |
| C2 H4 OCOCH3 |
| C2 H4 OCOCH3 |
| H NHCOCH3 |
| blueish violet |
| 38 p-ClC6 H4 |
| C2 H4 CN |
| ##STR8## H NHCOC6 H5 |
| blueish violet |
| 39 p-ClC6 H4 |
| C2 H4 CN |
| CH2 CHCH2 |
| OCH3 |
| NHCOCH3 |
| greenish blue |
| 40 p-ClC6 H4 |
| CH2 CHCH2 |
| CH2 CHCH2 |
| OCH3 |
| NHCOCH3 |
| greenish blue |
| 41 p-CH3C6 H4 |
| C2 H5 |
| C2 H5 |
| H NHCOCH3 |
| blue |
| 42 p-CH3C6 H4 |
| CH2 CHCH2 |
| CH2 CHCH2 |
| H NHCOCH3 |
| blue |
| 43 p-CH3C6 H4 |
| C 4 H9 (n) |
| C4 H9 (n) |
| H NHCOCH3 |
| blue |
| 44 p-CH3C6 H4 |
| C6 H13 (n) |
| C6 H13 (n) |
| H NHCOCH3 |
| blue |
| 45 p-CH3C6 H4 |
| CH2 CHCH2 |
| CH2 CHCH2 |
| H NHCOC2 H5 |
| blue |
| 46 p-CH3C6 H4 |
| C2 H4 CN |
| CH2 CHCH2 |
| OCH3 |
| NHCOCH3 |
| greenish blue |
| 47 p-CH3C6 H4 |
| C2 H4 OCOCH3 |
| C2 H4 OCOCH3 |
| OCH3 |
| NHCOCH3 |
| greenish blue |
| 48 o,p-(CH3)2C6 H3 |
| C2 H5 |
| C2 H5 |
| H NHCOCH3 |
| blue |
| 49 o,p-(CH3)2C6 H3 |
| C4 H9 (n) |
| C4 H9 (n) |
| H NHCOCH3 |
| blue |
| 50 o,p-(CH3)2C6 H3 |
| CH2 CHCH2 |
| CH2 CHCH2 |
| H NHCOCH3 |
| blue |
| 51 o,p-(CH3)2C6 H3 |
| C6 H13 (n) |
| C6 H13 (n) |
| H NHCOCH3 |
| blue |
| 52 o,p-(CH3)2 C6 H3 |
| C2 H4 OCOCH3 |
| C2 H4 OCOCH3 |
| H NHCOC6 H5 |
| blue |
| 53 o,p-(CH3)2C6 H3 |
| C2 H4 CN |
| CH2 CHCH2 |
| OCH3 |
| NHCOCH3 |
| blue |
| 54 |
| ##STR9## C2 H5 |
| C2 H5 |
| H NHCOCH3 |
| blue |
| 55 |
| ##STR10## C4 H9 (n) |
| C4 H9 (n) |
| H NHCOCH3 |
| blue |
| 56 |
| ##STR11## C6 H13 (n) |
| C6 H13 (n) |
| H NHCOCH3 |
| blue |
| 57 C6 H5 |
| C2 H5 |
| C2 H5 |
| H NHCOCH2 OCH3 |
| blue |
| 58 C6 H5 |
| C3 H7 (n) |
| C3 H7 (n) |
| H NHCOCH2 OCH3 |
| blue |
| 59 C6 H5 |
| C4 H9 (n) |
| C4 H9 (n) |
| H NHCOCH2 OCH3 |
| blue |
| 60 C6 H5 |
| C2 H5 |
| C2 H5 |
| H NHCOCH2 OC2 |
| blueb.5 |
| 61 C6 H 5 |
| C2 H5 |
| C2 H5 |
| H NHCOCH2 Cl |
| blue |
| 62 C6 H5 |
| C2 H5 |
| C2 H5 |
| H NHCOCH2 CN |
| blue |
| 63 C6 H5 |
| C2 H5 |
| C2 H5 |
| H NHCOCH2 OC6 |
| blueb.5 |
| __________________________________________________________________________ |
Hahn, Erwin, Hansen, Guenter, Reichelt, Helmut, Bergmann, Udo
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| Mar 11 1986 | HAHN, ERWIN | BASF Aktiengesellschaft | ASSIGNMENT OF ASSIGNORS INTEREST | 004838 | /0211 | |
| Mar 11 1986 | HANSEN, GUENTER | BASF Aktiengesellschaft | ASSIGNMENT OF ASSIGNORS INTEREST | 004838 | /0211 | |
| Mar 11 1986 | REICHELT, HELMUT | BASF Aktiengesellschaft | ASSIGNMENT OF ASSIGNORS INTEREST | 004838 | /0211 | |
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